US5550236A - Process for cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates - Google Patents

Process for cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates Download PDF

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US5550236A
US5550236A US08/424,254 US42425495A US5550236A US 5550236 A US5550236 A US 5550236A US 42425495 A US42425495 A US 42425495A US 5550236 A US5550236 A US 5550236A
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Hubert Schlosser
Rainer Wingen
Javier Manero
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/30—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
    • C09K19/3458—Uncondensed pyrimidines
    • C09K19/3466—Pyrimidine with at least another heterocycle in the chain

Definitions

  • the invention relates to a process for preparing polycyclic aromatic compounds by cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates catalyzed by metallic palladium, if desired applied to a support material.
  • Aromatic boron compounds too such as boronic acids and their derivatives or boranes, have already been used for coupling with aromatic halogen compounds or perfluoroalkylsulfonates (see, for example, B. N. Miyaura, T. Yanagi, A. Suzuki in Synthetic Communications 11 (1981), p. 513 ff.; M. J. Sharp, W. Cheng, V. Snieckus in Tetrahedron Letters 28 (1987), p. 5093 ff.; G. W. Gray in J. Chem. Soc. Perkin Trans II, 1989, p. 2041 ff. and Mol. Cryst, Sig. Cryst, 172 (1989), p. 165 ff., 204 (1991), p. 43 ff and p. 91 ff.; EP 0 449 015; WO 89/12039; WO 89/03821; EP 0 354 434).
  • EP-A-0 152 450 describes the coupling of Grignard reagents under heterogeneous Pd(0) catalysis.
  • the German Patent 3 930 663 describes a process for preparing liquid-crystalline compounds in which halides and organometallic compounds, including boronic acids, are reacted in inert solvents using metallic palladium, if desired applied to a support material, as catalyst, if desired in the presence of a metal alkoxide.
  • the invention accordingly provides a process for preparing polycyclic aromatic compounds by cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates in the presence of metallic palladium, if desired applied to a support material, as catalyst, wherein the coupling is carried out in the presence of a ligand and a base.
  • the coupling reaction proceeds chemoselectively, so that even electrophilic groups such as esters or nitriles do not impair the course of the reaction.
  • the catalyst system used in this process comprising metallic palladium, if desired applied to a support material, and a ligand, is derived from components which are commercially available at low cost and which allow economical operation of the process.
  • the palladium metal obtained as a solid after the reaction is complete can be easily separated off, regenerated and recycled to the catalyst process, which achieves an additional lowering of the process costs and avoids contamination of the waste products by palladium.
  • catalytic amounts of a ligand allows the yield of polycyclic aromatic compounds to be significantly increased in comparison with processes not using a ligand and thus allows a yield optimum for the Pd(0)-catalyzed cross-coupling of aromatic boronic acids with aromatic halogen compounds to be achieved.
  • the aromatic boronic acid, the aromatic halogen compound or the perfluoroalkylsulfonate, the base, the catalytic amount of metallic palladium, if desired applied to a support material, and the catalytic amount of a ligand are preferably added to an inert solvent or inert solvent mixture and stirred at a temperature of from 0° C. to 200° C., preferably at from 30° C. to 170° C., particularly preferably at from 50° C.
  • the Pd catalyst obtained as solid is separated off by filtration, the crude product is freed of the solvent or the solvents and is subsequently purified by methods known to those skilled in the art and matched to the respective product, e.g. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.
  • Solvents suitable for the process of the invention are, for example, ethers, e.g. diethyl ether, dimethoxymethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether, tert-butyl methyl ether, hydrocarbons, e.g. hexane, iso-hexane, heptane, cyclohexane, benzene, toluene, xylene, alcohols, e.g.
  • methanol ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol, tert-butanol, ketones, e.g. acetone, ethyl methyl ketone, iso-butyl methyl ketone, amides, e.g. dimethylformamide, dimethylacetamide, N-methylpyrrolidone, nitriles, e.g. acetonitrile, propionitrile, butyronitrile, water and mixtures of the same.
  • ketones e.g. acetone, ethyl methyl ketone, iso-butyl methyl ketone
  • amides e.g. dimethylformamide, dimethylacetamide, N-methylpyrrolidone
  • nitriles e.g. acetonitrile, propionitrile, butyronitrile, water and mixtures of the same.
  • Preferred solvents are ethers such as dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether, hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene, xylene, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, ketones such as ethyl methyl ketone, iso-butyl methyl ketone, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, water and mixtures of the same.
  • ethers such as dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether
  • hydrocarbons such
  • Particularly preferred solvents are ethers, e.g. dimethoxyethane, tetrahydrofuran, hydrocarbons, e.g. cyclohexane, benzene, toluene, xylene, alcohols, e.g. ethanol, 1-propanol, 2-propanol, water and mixtures of the same.
  • dimethoxyethane benzene, toluene, ethanol, water and mixtures of the same.
  • Bases which are preferably used in the process of the invention are alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali metal and alkaline earth metal acetates, alkali metal and alkaline earth metal alkoxides, and also primary, secondary and tertiary amines.
  • alkali metal and alkaline earth metal hydroxides are particularly preferred.
  • alkali metal and alkaline earth metal carbonates and alkali metal hydrogen carbonates are particularly preferred.
  • alkali metal hydroxides, alkali metal carbonates and alkali metal hydrogen carbonates such as lithium carbonate, sodium carbonate, potassium carbonate.
  • the base is preferably used in the process of the invention in a proportion of from 100 to 1000 mol %, particularly preferably from 100 to 500 mol %, very particularly preferably from 150 to 400 mol %, in particular from 180 to 250 mol %, based on the aromatic boronic acid.
  • the catalyst used is metallic palladium, preferably palladium in powdered form or on a support material, e.g. palladium on activated carbon, palladium on aluminum oxide, palladium on barium carbonate, palladium on barium sulfate, palladium on aluminum silicates such as montmorillonite, palladium on SiO 2 and palladium on calcium carbonate, in each case having a palladium content of from 0.5 to 10% by weight, particularly preferably palladium in powdered form and also palladium on activated carbon, palladium on barium and calcium carbonate, and palladium on barium sulfate, in each case having a palladium content of from 0.5 to 10% by weight, in particular palladium on activated carbon having a palladium content of 10% by weight.
  • a support material e.g. palladium on activated carbon, palladium on aluminum oxide, palladium on barium carbonate, palladium on barium sulfate, palladium on
  • catalysts which contain further dopants e.g. lead (Lindlar catalyst), in addition to palladium and the supporting material.
  • the metallic palladium catalyst is used in the process of the invention in a proportion of from 0.1 to 10 mol %, preferably from 0.2 to 5 mol %, particularly preferably from 0.5 to 3 mol %, most particularly preferably from 0.5 to 1.5 mol %, based on the aromatic halogen compound or the perfluoroalkylsulfonate.
  • Suitable ligands for the process of the invention are, for example, phosphines such as trialkylphosphines, tricycloalkylphosphines, triarylphosphines, where the three substituents on the phosphorus can be identical or different, chiral or achiral and where one or more of the ligands can link the phosphorus groups of a plurality of phosphines and where a part of this linkage can also be one or more metal atoms.
  • phosphines such as trialkylphosphines, tricycloalkylphosphines, triarylphosphines, where the three substituents on the phosphorus can be identical or different, chiral or achiral and where one or more of the ligands can link the phosphorus groups of a plurality of phosphines and where a part of this linkage can also be one or more metal atoms.
  • phosphines which can be used for the purposes of the process of the invention are trimethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tritolylphosphine, tris(4-dimethylaminophenyl)phosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and 1,1'-bis(diphenylphosphino)ferrocene.
  • Further suitable ligands are, for example, diketones, e.g. acetylacetone and octafluoroacetylacetone and tertiary amines, e.g. trimethylamine, triethylamine, tri-n-propylamine and triisopropylamine.
  • Preferred ligands are phosphines and diketones, particular preference being given to phosphines.
  • Very particularly preferred ligands are triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and 1,1'-bis(diphenylphosphino)ferrocene, in particular triphenylphosphine.
  • the ligand is used in the process of the invention in a proportion of from 0.1 to 20 mol %, preferably from 0.2 to 15 mol %, particularly preferably from 0.5 to 10 mol %, most particularly preferably from 1 to 6 mol %, based on the aromatic halogen compound or the perfluoroalkylsulfonate.
  • One class of starting compounds for the process of the invention consists of aromatic boronic acids, preferably those of the formula II,
  • R 1 , A 1 , A 2 , M 1 , k and l are as defined below:
  • R 1 is benzyloxy, H, F, Cl, Br, --NC, --CN, --CF 3 , --OCF 3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH 2 -- groups can also be replaced by --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO-O--, --CH--CH--, --C.tbd.C--, or --Si(CH 3 ) 2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl, Br or CN,
  • a 1 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, trans-1,4-cyclohexylene, where one or two nonadjacent CH 2 groups can be replaced by --O-- or --S-- and where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, (1,3,4)-thiadiazole-2,5-diyl, 1,3-thiazol-2,4-diyl, 1,3-thiazol-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, piperazine-1,4-diyl, piperazine-2,
  • a 2 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, 1,3,4-thiadiazole-2,5-diyl, 1,3-thiazol-2,4-diyl, 1,3-thiazol-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl or naphthalene-2,6-diyl,
  • M 1 is --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO--O--, --CH 2 --O--, --OCH 2 --, --CH 2 CH 2 --, --CH ⁇ CH--, --C.tbd.C--, --CH(CN)--CH 2 --, --CH 2 --CH(CN)--, --CH ⁇ N--, --N ⁇ CH--, --CH 2 CH 2 CH 2 --O--, --OCH 2 CH 2 --, --CH 2 CH 2 CO--O--, --O--COCH 2 CH 2 -- and
  • k, l are each, independently of one another, zero or one.
  • R 1 is benzyloxy, H, F, Cl, --CF 3 , OCF 3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH 2 -- groups can also be replaced by --O--, --CO--, --CO--O--, --OCO--, --O--CO--O--, --CH ⁇ CH--, --C.tbd.C--, or --Si(CH 3 ) 2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl or CN.
  • R 1 is benzyloxy, H or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH 2 -- groups can also be replaced by --O--, --CH ⁇ CH--, --C.tbd.C--, or --Si(CH 3 ) 2 --.
  • a 1 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, trans-1,4-cyclohexylene where one or two nonadjacent --CH 2 -- groups can be replaced by --O--, (1,3,4)-thiadiazol-2,5-diyl, naphthalene-2,6-diyl or bicyclo[2.2.2]octane-1,4-diyl.
  • a 1 is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, and also pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by fluorine, or trans-1,4-cyclohexylene.
  • a 2 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, or naphthalene-2,6-diyl.
  • a 2 is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, and also pyridine-2,5-diyl where one or two hydrogen atoms can be replaced by F, or naphthalene-2,6-diyl.
  • M 1 is --O--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --CH 2 --O--, --O--CH 2 --, --CH 2 --CH 2 --, --CH ⁇ CH--, --C.tbd.C--, --CH 2 CH 2 CH 2 --O--, --O--CH 2 CH 2 CH 2 --, --CH 2 CH 2 CO--O-- or --O--CO--CH 2 CH 2 --.
  • M 1 is --O--, --CH 2 --O--, --O--CH 2 --, --CH 2 --CH 2 --, --CH ⁇ CH-- or --C.tbd.C--.
  • aromatic boronic acids used preferably those of th e formula II
  • aromatic boronic acids are either known or can be prepared by known methods, as described, for example, in Houben Weyl Methoden der Organischen Chemie, Georg Thieme-Verlag, Stuttgart, Volume 13/3a.
  • boronic acids preferably those of the formula II, from aromatic alkali metal and magnesium compounds by reaction with trialkoxyboranes and subsequent hydrolysis.
  • the second class of starting compounds for the process of the invention consists of aromatic halogen compounds or aromatic perfluoroalkylsulfonates, preferably those of the formula III,
  • R 2 , A 3 , A 4 , M 2 , X, m and n are as defined below.
  • R 2 ie benzyloxy, H, F, Cl, Br, --NC, --CN, --CF 3 , --OCF 3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH 2 -- groups can also be replaced by --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO-O--, --CH ⁇ CH--, --C.tbd.C--, or --Si(CH 3 ) 2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl, Br or CN,
  • a 4 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, trans-1,4-cyclohexylene, where one or two nonadjacent CH 2 groups can be replaced by --O-- or --S-- and where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, (1,3,4)-thiadiazole-2,5-diyl, 1,3-thiazol-2,4-diyl, 1,3-thiazol-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, piperazine-1,4-diyl, piperazine-2,
  • a 3 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can also be replaced by halogen atoms, cyano and/or methyl groups, 1,3,4-thiadiazole-2,5-diyl, 1,3-thiazol-2,4-diyl, 1,3-thiazol-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl or naphthalene-2,6-diyl,
  • M 2 is --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO--O--, --CH 2 --O--, --OCH 2 --, --CH 2 CH 2 --, --CH ⁇ CH--, --C.tbd.C--, --CH(CN)--CH 2 --, --CH 2 --CH(CN)--, --CH ⁇ N--, --N ⁇ CH--, --CH 2 CH 2 CH 2 --O--, --OCH 2 CH 2 --, --CH 2 CH 2 CO--O--, --O--COCH 2 CH 2 -- and
  • n are each, independently of one another, zero or one.
  • R 2 is benzyloxy, H, F, Cl, Br, --CN, --CF 3 , OCF 3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH 2 -- groups can also be replaced by --O--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --CH ⁇ CH--, --C.tbd.C--, or --Si(CH 3 ) 2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl or CN.
  • R 2 is benzyloxy, H, Cl, Br or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH 2 -- groups can also be replaced by --O--, --CO--, --CO--O--, --O--, --O--CO--, --O--CO--O--, --CH ⁇ CH--, --C.tbd.C--, or --Si(CH 3 )--.
  • a 3 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, 1,3,4-thiadiazol-2,5-diyl or naphthalene-2,6-diyl.
  • a 3 is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, and also pyrazine-2,5-diyl, pyridazine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms or naphthalene-2,6-diyl.
  • a 4 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, trans-1,4-cyclohexylene, where one or two nonadjacent CH 2 groups can be replaced by --O--, (1,3,4)-thiadiazole-2,5-diyl, naphthalene-2,6-diyl or bicyclo[2.2.2]octane-1,4-diyl.
  • a 4 is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, and also pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by F, or trans-1,4-cyclohexylene.
  • M 2 is --O--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --CH 2 --O--, --O--CH 2 --, --CH 2 --CH 2 --, --CH ⁇ CH--, --C.tbd.C--, --CH 2 CH 2 CH 2 --O--, --O--CH 2 CH 2 CH 2 --, --CH 2 CH 2 CO--O-- or --O--CO--CH 2 CH 2 --.
  • M 2 is --O--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --CH 2 --O--, --O--CH 2 --, --CH 2 --CH 2 --, --CH--CH--, --C.tbd.C--, --CH 2 CH 2 CH 2 --O--, --O--CH 2 CH 2 CH 2 --, --CH 2 CH 2 CO--O-- or --O--CO--CH 2 CH 2 .
  • X is chlorine, bromine or OSO 2 --C p F 2p+1 , where p is an integer from 1 to 10.
  • X is chlorine or bromine.
  • aromatic halogen compounds and perfluoroalkylsulfonates preferably those of the general formula III, are either known or can be prepared by known methods, as are described, for example, in Houben Weyl, Methoden der Organischen Chemie, Georg Thieme-Verlag, Stuttgart, Volume 5/3 and 5/4.
  • the aromatic halides can be obtained by replacing the diazonium group in a corresponding diazonium salt by chlorine, bromine or iodine.
  • hydroxy-substituted nitrogen heterocycles can be converted by means of phosphorus trihalides and phosphorus oxytrihalides into the corresponding halides.
  • the process of the invention for cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates can likewise be used for preparing compounds of the formula III.
  • Perfluoroalkylsulfonates of the formula III, where X is OSO 2 --C n H 2n+1 can be prepared by esterification of corresponding alcohols of the formula III, where X is a hydroxyl group, with perfluoroalkanesulfonic acids or their reactive derivatives.
  • the corresponding perfluoroalkanesulfonic acids are known.
  • Suitable reactive derivatives of the said perfluoroalkanesulfonic acids are, in particular, the acid halides, especially the chlorides and bromides, also the anhydrides.
  • Products of the process of the invention are polycyclic aromatic compounds.
  • Preferred products of the process of the invention are compounds of the formula I,
  • R 1 and R 2 can be, independently of one another, benzyloxy, H, F, Cl, Br, --NC, --CN, --CF 3 , --OCF 3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH 2 groups can also replaced by --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO-O--, --CH ⁇ CH--, --C.tbd.C--, or --Si(CH 3 ) 2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl, Br or CN,
  • a 1 and A 4 can each be, independently of one another, 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, trans-1,4-cyclohexylene where one or two nonadjacent CH 2 groups can be replaced by --O-- or --S-- and where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, (1,3,4)-thiadiazole-2,5-diyl, 1,3-thiadiazole-2,4-diyl, 1,3-thiazole-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, piperazine-1,4
  • a 2 and A 3 can each be, independently of one another, 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, 1,3,4-thiadiazole-2,5-diyl, 1,3-thiazole-2,4-diyl, 1,3-thiazole-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl or naphthalene-2,6-diyl,
  • M 1 and M 2 can each be, independently of one another, --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S, --S--CO--, --O--CO--O--, --CH 2 --O--, --OCH 2 --, --CH 2 CH 2 --, --CH ⁇ CH--, --C.tbd.C--, --CH(CN)--CH 2 --, --CH 2 --CH(CN)--, --CH ⁇ N--, --N ⁇ CH--, --CH 2 CH 2 CH 2 --O--, --OCH 2 CH 2 CH 2 --, --CH 2 CH 2 CO--O--, --O--COCH 2 CH 2 --,
  • k, l, m, n are each, independently of one another, zero or one.
  • R 1 , R 2 , A 1 , A 2 , A 3 , A 4 , M 1 , M 2 , k, l, m, n are specified in the formulae II and III.
  • R 1 and R 2 are benzyloxy, H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl, and also methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy and pentadecoxy.
  • the compounds of the formula I are suitable for use as liquid-crystalline materials, or can be used as intermediates for the preparation of further liquid-crystalline compounds. Furthermore, compounds of the formula I are also suitable as precursors for pharmaceuticals, cosmetics, fungicides, herbicides, insecticides, dyes, detergents and polymers, including additives for the same.

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Abstract

A process for preparing polycyclic aromatic compounds by cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates in the presence of metallic palladium, if desired applied to a support material, as catalyst, wherein the coupling is carried out in the presence of a ligand and a base. The process of the invention allows the yield of polycyclic aromatic compounds to be significantly increased in comparison with processes not using a ligand and thus allows a yield optimum for the Pd(0)-catalyzed cross-coupling of aromatic boronic acids with aromatic halogen compounds to be achieved.

Description

The invention relates to a process for preparing polycyclic aromatic compounds by cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates catalyzed by metallic palladium, if desired applied to a support material.
The palladium-catalyzed cross-coupling reaction of terminal alkynes and organometallic alkyl, alkenyl, allyl or aryl compounds with alkyl, alkenyl, allyl or aryl halides or sulfonates has been utilized to an increasing extent in many areas of organic synthesis for some years (see, for example B. M. Trost, T. R. Verhoeven in: Comprehensive Organometallic Chemistry Volume 8, p. 779 ff., Pergamon Press, Oxford 19 . . . ).
The cross-coupling of metallated aryls with aromatic halides has been carried out, for example, using Grignard and organolithium reagents (see, for example, J.-F. Fauvarque and A. Jutard, Bull. Chim. Soc. Fr., 1976, 765, A. Sekiya and N. Ishikawa, J. Organomet. Chem., 1976, 118, 349, A. Sekija and N. Ishikawa, J. Organomet. Chem., 1977, 125, 281, M. Yamamura, I. Moritani and S. I. Murahashi, J. Organomet. Chem., 1975, 91, C39, S. I. Murahashi, M. Yamamura, K. Yanagiswa, N. Mira and K. Kondo, J. Org. Chem., 1979, 44, 2408, A. Minato, K. Tamao, T. Hayashi, K. Suzuki and M. Kumada, Tetrahedron Lett., 1980, 845.), organozinc reagents (for example, E. Negishi et al. J. Org. Chem. 42 (1977) 1822. ) and organotin reagents (for example, M. Kosogi et al., Chem. Lett. 1977, 301.).
Aromatic boron compounds too, such as boronic acids and their derivatives or boranes, have already been used for coupling with aromatic halogen compounds or perfluoroalkylsulfonates (see, for example, B. N. Miyaura, T. Yanagi, A. Suzuki in Synthetic Communications 11 (1981), p. 513 ff.; M. J. Sharp, W. Cheng, V. Snieckus in Tetrahedron Letters 28 (1987), p. 5093 ff.; G. W. Gray in J. Chem. Soc. Perkin Trans II, 1989, p. 2041 ff. and Mol. Cryst, Sig. Cryst, 172 (1989), p. 165 ff., 204 (1991), p. 43 ff and p. 91 ff.; EP 0 449 015; WO 89/12039; WO 89/03821; EP 0 354 434).
All these processes are homogeneously catalyzed processes using Pd(0) complexes, in particular tetrakis(triphenylphosphine)palladium(0).
However, the disadvantage of these processes is clearly in the high catalyst costs which make difficult the economical transfer of the processes to a larger production scale (kg, t). The homogeneous reaction procedure furthermore makes difficult an efficient regeneration of the palladium catalyst and can easily lead to contamination of the waste formed in the reaction with palladium.
For this reason, processes have been developed which circumvent these problems by heterogeneous use of the catalyst. EP-A-0 152 450 describes the coupling of Grignard reagents under heterogeneous Pd(0) catalysis. However, owing to the high reactivity of the organomagnesium component, the selection of starting materials for this process is severely limited. The German Patent 3 930 663 describes a process for preparing liquid-crystalline compounds in which halides and organometallic compounds, including boronic acids, are reacted in inert solvents using metallic palladium, if desired applied to a support material, as catalyst, if desired in the presence of a metal alkoxide. Although this procedure can substantially reduce the catalyst costs and the palladium can easily be regenerated after the reactions are complete, this process often gives the desired coupling product in only unsatisfactory yields.
It is therefore an object of the present invention to find a process for coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates, which process does not have the disadvantages described for the previous processes.
It has surprisingly been found that in the reaction of aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates in the presence of a base and catalytic amounts of metallic palladium, if desired applied to a support material, excellent yields of polycyclic aromatic compounds can be obtained by addition of catalytic amounts of a ligand.
The invention accordingly provides a process for preparing polycyclic aromatic compounds by cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates in the presence of metallic palladium, if desired applied to a support material, as catalyst, wherein the coupling is carried out in the presence of a ligand and a base.
The coupling reaction proceeds chemoselectively, so that even electrophilic groups such as esters or nitriles do not impair the course of the reaction.
The catalyst system used in this process, comprising metallic palladium, if desired applied to a support material, and a ligand, is derived from components which are commercially available at low cost and which allow economical operation of the process. In addition, the palladium metal obtained as a solid after the reaction is complete can be easily separated off, regenerated and recycled to the catalyst process, which achieves an additional lowering of the process costs and avoids contamination of the waste products by palladium.
The addition according to the invention of catalytic amounts of a ligand allows the yield of polycyclic aromatic compounds to be significantly increased in comparison with processes not using a ligand and thus allows a yield optimum for the Pd(0)-catalyzed cross-coupling of aromatic boronic acids with aromatic halogen compounds to be achieved.
To carry out the process of the invention, the aromatic boronic acid, the aromatic halogen compound or the perfluoroalkylsulfonate, the base, the catalytic amount of metallic palladium, if desired applied to a support material, and the catalytic amount of a ligand are preferably added to an inert solvent or inert solvent mixture and stirred at a temperature of from 0° C. to 200° C., preferably at from 30° C. to 170° C., particularly preferably at from 50° C. to 150° C., most particularly preferably at from 60° to 120° C., for a period of from 1 hour to 100 hours, preferably from 5 hours to 70 hours, particularly preferably from 10 hours to 50 hours, most particularly preferably from 15 hours to 30 hours. After the reaction is complete, the Pd catalyst obtained as solid is separated off by filtration, the crude product is freed of the solvent or the solvents and is subsequently purified by methods known to those skilled in the art and matched to the respective product, e.g. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.
Solvents suitable for the process of the invention are, for example, ethers, e.g. diethyl ether, dimethoxymethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether, tert-butyl methyl ether, hydrocarbons, e.g. hexane, iso-hexane, heptane, cyclohexane, benzene, toluene, xylene, alcohols, e.g. methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol, tert-butanol, ketones, e.g. acetone, ethyl methyl ketone, iso-butyl methyl ketone, amides, e.g. dimethylformamide, dimethylacetamide, N-methylpyrrolidone, nitriles, e.g. acetonitrile, propionitrile, butyronitrile, water and mixtures of the same.
Preferred solvents are ethers such as dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether, hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene, xylene, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, ketones such as ethyl methyl ketone, iso-butyl methyl ketone, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, water and mixtures of the same.
Particularly preferred solvents are ethers, e.g. dimethoxyethane, tetrahydrofuran, hydrocarbons, e.g. cyclohexane, benzene, toluene, xylene, alcohols, e.g. ethanol, 1-propanol, 2-propanol, water and mixtures of the same.
Most particularly preferred are dimethoxyethane, benzene, toluene, ethanol, water and mixtures of the same.
Bases which are preferably used in the process of the invention are alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali metal and alkaline earth metal acetates, alkali metal and alkaline earth metal alkoxides, and also primary, secondary and tertiary amines.
Particularly preferred are alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates and alkali metal hydrogen carbonates. Most particularly preferred are alkali metal hydroxides, alkali metal carbonates and alkali metal hydrogen carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate.
The base is preferably used in the process of the invention in a proportion of from 100 to 1000 mol %, particularly preferably from 100 to 500 mol %, very particularly preferably from 150 to 400 mol %, in particular from 180 to 250 mol %, based on the aromatic boronic acid.
The catalyst used is metallic palladium, preferably palladium in powdered form or on a support material, e.g. palladium on activated carbon, palladium on aluminum oxide, palladium on barium carbonate, palladium on barium sulfate, palladium on aluminum silicates such as montmorillonite, palladium on SiO2 and palladium on calcium carbonate, in each case having a palladium content of from 0.5 to 10% by weight, particularly preferably palladium in powdered form and also palladium on activated carbon, palladium on barium and calcium carbonate, and palladium on barium sulfate, in each case having a palladium content of from 0.5 to 10% by weight, in particular palladium on activated carbon having a palladium content of 10% by weight.
It is also possible to use catalysts which contain further dopants, e.g. lead (Lindlar catalyst), in addition to palladium and the supporting material.
The metallic palladium catalyst is used in the process of the invention in a proportion of from 0.1 to 10 mol %, preferably from 0.2 to 5 mol %, particularly preferably from 0.5 to 3 mol %, most particularly preferably from 0.5 to 1.5 mol %, based on the aromatic halogen compound or the perfluoroalkylsulfonate.
Suitable ligands for the process of the invention are, for example, phosphines such as trialkylphosphines, tricycloalkylphosphines, triarylphosphines, where the three substituents on the phosphorus can be identical or different, chiral or achiral and where one or more of the ligands can link the phosphorus groups of a plurality of phosphines and where a part of this linkage can also be one or more metal atoms.
Examples of phosphines which can be used for the purposes of the process of the invention are trimethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tritolylphosphine, tris(4-dimethylaminophenyl)phosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and 1,1'-bis(diphenylphosphino)ferrocene. Further suitable ligands are, for example, diketones, e.g. acetylacetone and octafluoroacetylacetone and tertiary amines, e.g. trimethylamine, triethylamine, tri-n-propylamine and triisopropylamine.
Preferred ligands are phosphines and diketones, particular preference being given to phosphines. Very particularly preferred ligands are triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and 1,1'-bis(diphenylphosphino)ferrocene, in particular triphenylphosphine. The ligand is used in the process of the invention in a proportion of from 0.1 to 20 mol %, preferably from 0.2 to 15 mol %, particularly preferably from 0.5 to 10 mol %, most particularly preferably from 1 to 6 mol %, based on the aromatic halogen compound or the perfluoroalkylsulfonate.
It is also possible, if desired, to use mixtures of two or more different ligands.
One class of starting compounds for the process of the invention consists of aromatic boronic acids, preferably those of the formula II,
R.sup.1 (--A.sup.1).sub.k (--M.sup.1).sub.l --A.sup.2 --B(OH).sub.2 (II)
where R1, A1, A2, M1, k and l are as defined below:
R1 is benzyloxy, H, F, Cl, Br, --NC, --CN, --CF3, --OCF3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH2 -- groups can also be replaced by --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO--O--, --CH--CH--, --C.tbd.C--, or --Si(CH3)2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl, Br or CN,
A1 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, trans-1,4-cyclohexylene, where one or two nonadjacent CH2 groups can be replaced by --O-- or --S-- and where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, (1,3,4)-thiadiazole-2,5-diyl, 1,3-thiazol-2,4-diyl, 1,3-thiazol-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, piperazine-1,4-diyl, piperazine-2,5-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, bicyclo[2.2.2]octane-1,4-diyl, 1,3-dioxaborinane-2,5-diyl or trans-decalin-2,6-diyl,
A2 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, 1,3,4-thiadiazole-2,5-diyl, 1,3-thiazol-2,4-diyl, 1,3-thiazol-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl or naphthalene-2,6-diyl,
M1 is --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO--O--, --CH2 --O--, --OCH2 --, --CH2 CH2 --, --CH═CH--, --C.tbd.C--, --CH(CN)--CH2 --, --CH2 --CH(CN)--, --CH═N--, --N═CH--, --CH2 CH2 CH2 --O--, --OCH2 CH2 CH2 --, --CH2 CH2 CO--O--, --O--COCH2 CH2 -- and
k, l are each, independently of one another, zero or one.
Preferably, R1 is benzyloxy, H, F, Cl, --CF3, OCF3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH2 -- groups can also be replaced by --O--, --CO--, --CO--O--, --OCO--, --O--CO--O--, --CH═CH--, --C.tbd.C--, or --Si(CH3)2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl or CN.
Particularly preferably, R1 is benzyloxy, H or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH2 -- groups can also be replaced by --O--, --CH═CH--, --C.tbd.C--, or --Si(CH3)2 --.
Preferably, A1 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, trans-1,4-cyclohexylene where one or two nonadjacent --CH2 -- groups can be replaced by --O--, (1,3,4)-thiadiazol-2,5-diyl, naphthalene-2,6-diyl or bicyclo[2.2.2]octane-1,4-diyl.
Particularly preferably, A1 is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, and also pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by fluorine, or trans-1,4-cyclohexylene.
Preferably, A2 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, or naphthalene-2,6-diyl.
Particularly preferably, A2 is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, and also pyridine-2,5-diyl where one or two hydrogen atoms can be replaced by F, or naphthalene-2,6-diyl.
Preferably, M1 is --O--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --CH2 --O--, --O--CH2 --, --CH2 --CH2 --, --CH═CH--, --C.tbd.C--, --CH2 CH2 CH2 --O--, --O--CH2 CH2 CH2 --, --CH2 CH2 CO--O-- or --O--CO--CH2 CH2 --.
Particularly preferably, M1 is --O--, --CH2 --O--, --O--CH2 --, --CH2 --CH2 --, --CH═CH-- or --C.tbd.C--.
Most particularly preferred are the aromatic boronic acids of the formulae IIa to IIh listed below: ##STR1## where R1 is benzyloxy, H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl, and also methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy and pentadecoxy.
The aromatic boronic acids used, preferably those of th e formula II, are either known or can be prepared by known methods, as described, for example, in Houben Weyl Methoden der Organischen Chemie, Georg Thieme-Verlag, Stuttgart, Volume 13/3a. Thus it is possible, for example, to obtain boronic acids, preferably those of the formula II, from aromatic alkali metal and magnesium compounds by reaction with trialkoxyboranes and subsequent hydrolysis.
The second class of starting compounds for the process of the invention consists of aromatic halogen compounds or aromatic perfluoroalkylsulfonates, preferably those of the formula III,
X--A.sup.3 (--M.sup.2).sub.m (--A.sup.4).sub.n --R.sup.2   (III)
where R2, A3, A4, M2, X, m and n are as defined below.
R2 ie benzyloxy, H, F, Cl, Br, --NC, --CN, --CF3, --OCF3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH2 -- groups can also be replaced by --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO--O--, --CH═CH--, --C.tbd.C--, or --Si(CH3)2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl, Br or CN,
A4 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, trans-1,4-cyclohexylene, where one or two nonadjacent CH2 groups can be replaced by --O-- or --S-- and where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, (1,3,4)-thiadiazole-2,5-diyl, 1,3-thiazol-2,4-diyl, 1,3-thiazol-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, piperazine-1,4-diyl, piperazine-2,5-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, bicyclo[2.2.2]octane-1,4-diyl, 1,3-dioxaborinane-2,5-diyl or trans-decalin-2,6-diyl,
A3 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can also be replaced by halogen atoms, cyano and/or methyl groups, 1,3,4-thiadiazole-2,5-diyl, 1,3-thiazol-2,4-diyl, 1,3-thiazol-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl or naphthalene-2,6-diyl,
M2 is --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO--O--, --CH2 --O--, --OCH2 --, --CH2 CH2 --, --CH═CH--, --C.tbd.C--, --CH(CN)--CH2 --, --CH2 --CH(CN)--, --CH═N--, --N═CH--, --CH2 CH2 CH2 --O--, --OCH2 CH2 CH2 --, --CH2 CH2 CO--O--, --O--COCH2 CH2 -- and
m, n are each, independently of one another, zero or one.
Preferably, R2 is benzyloxy, H, F, Cl, Br, --CN, --CF3, OCF3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH2 -- groups can also be replaced by --O--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --CH═CH--, --C.tbd.C--, or --Si(CH3)2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl or CN.
Particularly preferably, R2 is benzyloxy, H, Cl, Br or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH2 -- groups can also be replaced by --O--, --CO--, --CO--O--, --O--, --O--CO--, --O--CO--O--, --CH═CH--, --C.tbd.C--, or --Si(CH3)--.
Preferably, A3 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, 1,3,4-thiadiazol-2,5-diyl or naphthalene-2,6-diyl.
Particularly preferably, A3 is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, and also pyrazine-2,5-diyl, pyridazine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms or naphthalene-2,6-diyl.
Preferably, A4 is 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, trans-1,4-cyclohexylene, where one or two nonadjacent CH2 groups can be replaced by --O--, (1,3,4)-thiadiazole-2,5-diyl, naphthalene-2,6-diyl or bicyclo[2.2.2]octane-1,4-diyl.
Particularly preferably, A4 is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, and also pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by F, or trans-1,4-cyclohexylene.
Preferably, M2 is --O--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --CH2 --O--, --O--CH2 --, --CH2 --CH2 --, --CH═CH--, --C.tbd.C--, --CH2 CH2 CH2 --O--, --O--CH2 CH2 CH2 --, --CH2 CH2 CO--O-- or --O--CO--CH2 CH2 --.
Particularly preferably, M2 is --O--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --CH2 --O--, --O--CH2 --, --CH2 --CH2 --, --CH--CH--, --C.tbd.C--, --CH2 CH2 CH2 --O--, --O--CH2 CH2 CH2 --, --CH2 CH2 CO--O-- or --O--CO--CH2 CH2.
Preferably, X is chlorine, bromine or OSO2 --Cp F2p+1, where p is an integer from 1 to 10. Particularly preferably, X is chlorine or bromine.
Most particularly preferred are the aromatic halogen compounds of the formula III 1 to III 24 shown below, ##STR2## where R2 is benzyloxy, H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl, and also methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy and pentadecoxy.
The aromatic halogen compounds and perfluoroalkylsulfonates preferably those of the general formula III, are either known or can be prepared by known methods, as are described, for example, in Houben Weyl, Methoden der Organischen Chemie, Georg Thieme-Verlag, Stuttgart, Volume 5/3 and 5/4. For example, the aromatic halides can be obtained by replacing the diazonium group in a corresponding diazonium salt by chlorine, bromine or iodine.
Furthermore, hydroxy-substituted nitrogen heterocycles can be converted by means of phosphorus trihalides and phosphorus oxytrihalides into the corresponding halides. The process of the invention for cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates can likewise be used for preparing compounds of the formula III. Perfluoroalkylsulfonates of the formula III, where X is OSO2 --Cn H2n+1, can be prepared by esterification of corresponding alcohols of the formula III, where X is a hydroxyl group, with perfluoroalkanesulfonic acids or their reactive derivatives. The corresponding perfluoroalkanesulfonic acids are known. Suitable reactive derivatives of the said perfluoroalkanesulfonic acids are, in particular, the acid halides, especially the chlorides and bromides, also the anhydrides.
Products of the process of the invention are polycyclic aromatic compounds.
Preferred products of the process of the invention are compounds of the formula I,
R.sup.1 (--A.sup.1).sub.k (--M.sup.1).sub.l --A.sup.2 --A.sup.3 (--M.sup.2).sub.m (--A.sup.4).sub.n --R.sup.2             (I)
where R1 and R2 can be, independently of one another, benzyloxy, H, F, Cl, Br, --NC, --CN, --CF3, --OCF3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH2 groups can also replaced by --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO--O--, --CH═CH--, --C.tbd.C--, or --Si(CH3)2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl, Br or CN,
A1 and A4 can each be, independently of one another, 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, trans-1,4-cyclohexylene where one or two nonadjacent CH2 groups can be replaced by --O-- or --S-- and where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, (1,3,4)-thiadiazole-2,5-diyl, 1,3-thiadiazole-2,4-diyl, 1,3-thiazole-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, piperazine-1,4-diyl, piperazine-2,5-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, bicyclo[2.2.2]octane-1,4-diyl, 1,3-dioxaborinane-2,5-diyl or trans-decalin-2,6-diyl,
A2 and A3 can each be, independently of one another, 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, 1,3,4-thiadiazole-2,5-diyl, 1,3-thiazole-2,4-diyl, 1,3-thiazole-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl or naphthalene-2,6-diyl,
M1 and M2 can each be, independently of one another, --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S, --S--CO--, --O--CO--O--, --CH2 --O--, --OCH2 --, --CH2 CH2 --, --CH═CH--, --C.tbd.C--, --CH(CN)--CH2 --, --CH2 --CH(CN)--, --CH≡N--, --N═CH--, --CH2 CH2 CH2 --O--, --OCH2 CH2 CH2 --, --CH2 CH2 CO--O--, --O--COCH2 CH2 --,
and
k, l, m, n are each, independently of one another, zero or one.
Preferred and particularly preferred variants of R1, R2, A1, A2, A3, A4, M1, M2, k, l, m, n are specified in the formulae II and III.
Most particularly preferred are the compounds of the formula I 1 to I 94 shown below ##STR3## where R1 and R2 are benzyloxy, H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl, and also methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy and pentadecoxy.
The compounds of the formula I are suitable for use as liquid-crystalline materials, or can be used as intermediates for the preparation of further liquid-crystalline compounds. Furthermore, compounds of the formula I are also suitable as precursors for pharmaceuticals, cosmetics, fungicides, herbicides, insecticides, dyes, detergents and polymers, including additives for the same.
The present invention is illustrated by the Examples described below, without however being limited, where the abbreviations used have the following meanings:
mp.=melting point
X=crystalline
S=smectic
SC =smectic C
SA =smectic A
N=nematic
I=isotropic
EXAMPLE 1 5-Bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine
104.25 g (0.438 mol) of 2,5-dibromopyrimidine, 100.00 g (0.438 mol) of 4-(phenylmethoxy)benzeneboronic acid, 4.75 g (0.00438 mol) of palladium (10%) on activated carbon, 4.50 g (0.01752 mol) of triphenylphosphine and 93.00 g (0.876 mol) of sodium carbonate are heated in 1000 ml of toluene, 500 ml of ethanol and 300 ml of water for 24 hours at 80° C. The palladium catalyst is subsequently separated off from the reaction mixture at 80° C. by filtration. The aqueous lower phase of the reaction mixture is separated off at 80° C., before the organic phase is freed of the solvents on a rotary evaporator and dried in a high vacuum. The crude product thus obtained is recrystallized from acetonitrile (3000 ml), giving 150.07 g (97% yield, based on 2,5-dibromopyridine) of 5-bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine (purity according to HPLC: 98%). ##STR4## mp.: 153°-155° C.
COMPARATIVE EXAMPLE 1 Synthesis of 5-bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine by the process described in DE 39 30 663
4.17 g (17.54 mmol) of 2,5-dibromopyrimidine, 4.00 g (17.54 mmol) of 4-(phenylmethoxy)benzeneboronic acid, 0.19 g (0,175 mmol) of palladium (10%) on activated carbon and 3.72 g (35.10 mmol) of sodium carbonate are reacted in 42 ml of toluene, 21 ml of ethanol and 12.5 ml of water using a similar method to Example 1.
Analysis (HPLC) of the crude product indicates a mixture which contains the starting materials 2,5-dibromopyrimidine, 4-(phenylmethoxy)benzeneboronic acid and unidentified products in addition to 6.3% of the desired product 5-bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine.
  - Example No. R.sup.1 A.sup.1 A.sup.2 A.sup.3 A.sup.4 R.sup.2 Yield
 Phase transitions
  2 H.sub.17 C.sub.8
  O
 ##STR5##
  ##STR6##
   Br 97%
 3
  ##STR7##
  ##STR8##
  ##STR9##
   Br 99%
 4 H.sub.17 C.sub.8
  O
 ##STR10##
  ##STR11##
   Br 96%
 5 H
  ##STR12##
  ##STR13##
   Br 93%
 6 H.sub.13
  C.sub.6
 ##STR14##
  ##STR15##
  ##STR16##
  H 98 X 97 S.sub.A 133 I
 7 H.sub.13 C.sub.6
  O
 ##STR17##
  ##STR18##
  ##STR19##
  H 95% X 92 S.sub.A 163 I
 8 H.sub.13
  C.sub.6
 ##STR20##
  ##STR21##
  ##STR22##
  O(CH.sub.2).sub.4 CHCH2 90% X 70 S.sub.4 62 S.sub.3 108 S.sub.C 146
 S.sub.A 189 I
 9
  ##STR23##
  ##STR24##
  ##STR25##
   H 85%
 10 H.sub.17 C.sub.8
  O
 ##STR26##
  ##STR27##
   H 91%
 11 H.sub.17 C.sub.8
  O
 ##STR28##
  ##STR29##
   H 87%
 12 H.sub.17 C.sub.8
  O
 ##STR30##
  ##STR31##
   H 81%
 13 H
  ##STR32##
  ##STR33##
  ##STR34##
  O(CH.sub.2).sub.8
  CHCH2 92% X 96 S.sub.A 91
                   14
  ##STR35##
  ##STR36##
  ##STR37##
  ##STR38##
   Br 95%
 15 H.sub.17 C.sub.8
  O
 ##STR39##
  ##STR40##
  ##STR41##
   H 83% X 148 S.sub.3 149 S.sub.C 150 S.sub.A 162 I
 16 H.sub.17 C.sub.8
  O
 ##STR42##
  ##STR43##
  ##STR44##
   H 80% X 95 S.sub.3 111 S.sub.C 116 S.sub.A 132 I
 17 H.sub.7
  C.sub.3
 ##STR45##
  ##STR46##
  ##STR47##
   Br 93%
 18 H.sub.11
  C.sub.5
 ##STR48##
  ##STR49##
  ##STR50##
   Br 89%
 19 H.sub.17
  C.sub.8
 ##STR51##
  ##STR52##
  ##STR53##
   Br 90%
 20 H.sub.11
  C.sub.5
 ##STR54##
  ##STR55##
  ##STR56##
   H 85%
 21 H.sub.11
  C.sub.5
 ##STR57##
  ##STR58##
  ##STR59##
   H 82%
 22 H.sub.17 C.sub.8
  O
 ##STR60##
  ##STR61##
   Br 89%
 23 H.sub.2
  CCH(CH.sub.2).sub.8O
 ##STR62##
  ##STR63##
   Br 93%
 24 H.sub.17 C.sub.8
  O
 ##STR64##
  ##STR65##
   OC.sub.8
  H.sub.17 96% X 64 S.sub.C 67 S.sub.A 91 I
          25 H.sub.17 C.sub.8
  O
 ##STR66##
  ##STR67##
   O(CH.sub.2).sub.8
  CHCH2 80% X 59 S.sub.C 66 S.sub.A 80 I
                    26 H.sub.13 C.sub.6
  O
 ##STR68##
  ##STR69##
   O(CH.sub.2).sub.8
  CHCH2 83% X 56 S.sub.A 80 I
                    27 H.sub.21 C.sub.10
  O
 ##STR70##
  ##STR71##
   OC.sub.8
  H.sub.17 90% X 67 S.sub.C 74 S.sub.A 89 I
          28 H.sub.2
  CCH(CH.sub.2).sub.8O
 ##STR72##
  ##STR73##
   C.sub.8
  H.sub.17 94% X (65) S.sub.A 64 I
         29 H.sub.2
  CCH(CH.sub.2).sub.8O
 ##STR74##
  ##STR75##
  ##STR76##
  H 96% X 87 S.sub.A 125 I
 30 H
  ##STR77##
  ##STR78##
   Br 82%
 31 H
  ##STR79##
  ##STR80##
  ##STR81##
   OC.sub.10
  H.sub.21 90% X 125 S.sub.A 154 I
            32 H
  ##STR82##
  ##STR83##
  ##STR84##
   OC.sub.8
  H.sub.17 92% X 133 S.sub.A 153 I
          33 H
  ##STR85##
  ##STR86##
  ##STR87##
   Br 87%
 34 H.sub.17 C.sub.8
  O
 ##STR88##
  ##STR89##
  ##STR90##
  OC.sub.2
  H.sub.5 93% X 91 S.sub.C 100 S.sub.A 218 I
         35 H.sub.17 C.sub.8
  O
 ##STR91##
  ##STR92##
  ##STR93##
  OC.sub.8
  H.sub.17 96% X 91 S.sub.C 190 S.sub.A 194 I
         36 H.sub.17 C.sub.8
  O
 ##STR94##
  ##STR95##
  ##STR96##
  O(CH.sub.2).sub.9
  CHCH2 87% X 83 S.sub.C 175 S.sub.A 179 I
                   37 H.sub.17 C.sub.8
  O
 ##STR97##
  ##STR98##
  ##STR99##
  O(CH.sub.2).sub.2
  CHCH2 90% X 89 S.sub.C 159 S.sub.A 207 I
                   38 H.sub.17 C.sub.8
  O
 ##STR100##
  ##STR101##
   OC.sub.8
  H.sub.17 85%
          39 H.sub.17 C.sub.8
  O
 ##STR102##
  ##STR103##
  ##STR104##
  OC.sub.8 H.sub.17 92% X 87 S.sub.3 116 S.sub.C 158 S.sub.A 163 I
                                                                   40
 H.sub.13 C.sub.6
  O
 ##STR105##
  ##STR106##
  ##STR107##
  OC.sub.8 H.sub.17 96% X 85 S.sub.4 93 S.sub.3 119 S.sub.C 161 S.sub.A
 169 I
 41 H.sub.17 C.sub.8
  O
 ##STR108##
  ##STR109##
  ##STR110##
  C.sub.8
  H.sub.17 99% X 62 S.sub.3 96 S.sub.C 116 S.sub.A 133 I
        42 H.sub.13 C.sub.6
  O
 ##STR111##
  ##STR112##
  ##STR113##
  C.sub.8 H.sub.17 96% X 44 S.sub.4 92 S.sub.3 99 S.sub.C 118 S.sub.A 138
 I
 43 H.sub.17 C.sub.8
  O
 ##STR114##
  ##STR115##
  ##STR116##
  OC.sub.8
  H.sub.17 82% X 91 S.sub.A 95 I
         44 H.sub.17 C.sub.8
  O
 ##STR117##
  ##STR118##
  ##STR119##
  OC.sub.8
  H.sub.17 85% X 91 S.sub.C 110 S.sub.A 116 I
         45 H.sub.17 C.sub.8
  O
 ##STR120##
  ##STR121##
  ##STR122##
  OC.sub.8
  H.sub.17 81% X 124 I
         46 H.sub.17 C.sub.8
  O
 ##STR123##
  ##STR124##
  ##STR125##
  OC.sub.8
  H.sub.17 80% X 65 S.sub.C 85 S.sub.A 104 I
         47 H.sub.17 C.sub.8
  O
 ##STR126##
  ##STR127##
  ##STR128##
  OC.sub.8
  H.sub.17 87% X 100 S.sub.C 127 N 128 I
         48 H.sub.17 C.sub.8
  O
 ##STR129##
  ##STR130##
  ##STR131##
  C.sub.5
  H.sub.11 93% X 78 S.sub.A 110 N 117 I
        49 H.sub.21 C.sub.10
  O
 ##STR132##
  ##STR133##
  ##STR134##
  C.sub.5
  H.sub.11 89% X 64 S.sub.A 108 N 112 I
        50 H.sub.25 C.sub.12
  O
 ##STR135##
  ##STR136##
  ##STR137##
  C.sub.5
  H.sub.11 90% X 62 S.sub.A 104 N 107 I
        51 H.sub.17 C.sub.8
  O
 ##STR138##
  ##STR139##
   OC.sub.8
  H.sub.17 94% X 58 S.sub.A 86 I
          52 H.sub.17 C.sub.8
  O
 ##STR140##
  ##STR141##
  ##STR142##
   OC.sub.6
  H.sub.13 86% X 105 S.sub.C 174 N 188 I
          53 H.sub.17 C.sub.8
  O
 ##STR143##
  ##STR144##
  ##STR145##
   OC.sub.8
  H.sub.17 80% X 105 S.sub.C 176 N 182 I
          54 H.sub.17 C.sub.8
  O
 ##STR146##
  ##STR147##
  ##STR148##
   C.sub.7
  H.sub.15 81% X 58 S.sub.2 65 S.sub.C 157 N 164 I
         55 H.sub.17 C.sub.8
  O
 ##STR149##
  ##STR150##
  ##STR151##
   C.sub.6
  H.sub.13 83% X 55 S.sub.2 58 S.sub.C 153 N 163 I
         56 H.sub.17 C.sub.8
  O
 ##STR152##
  ##STR153##
  ##STR154##
   H 91%
 57 H
  ##STR155##
  ##STR156##
  ##STR157##
   OC.sub.8
  H.sub.17 86% X 107 (80) S.sub.A 85 N 101 I
          58 H.sub.17 C.sub.8
  O
 ##STR158##
  ##STR159##
  ##STR160##
  ##STR161##
  C.sub.8 H.sub.17 80% X 73 S.sub.3 173 S.sub.C 273 S.sub.A 275 N 281 I
 59 H.sub.17 C.sub.8
  O
 ##STR162##
  ##STR163##
   Br 97%
 60 H.sub.17 C.sub.8
  O
 ##STR164##
  ##STR165##
   H 92%

Claims (8)

We claim:
1. A process for preparing polycyclic aromatic compounds by cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates in the presence of metallic palladium, if desired applied to a support material, as catalyst, wherein the coupling is carried out in the presence of a ligand selected from the group consisting of phosphines, diketones and tertiary amines and a base.
2. The process as claimed in claim 1, wherein a polycyclic aromatic compound of the formula I
R.sup.1 (--A.sup.1).sub.k (--M.sup.1).sub.l --A.sup.2 --A.sup.3 (--M.sup.2).sub.m (--A.sup.4).sub.n --R.sup.2             (I)
where R1 and R2 can be, independently of one another, benzyloxy, H, F, Cl, Br, --NC, --CN, --CF3, --OCF3 or a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having from 1 to 18 carbon atoms, where one or two nonadjacent --CH2 groups can also be replaced by --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO--O--, --CH═CH--, --C.tbd.C--, or --Si(CH3)2 --, and where one or more hydrogen atoms of the alkyl radical can also be replaced by F, Cl, Br or CN, A1 and A4 can each be, independently of one another, 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, trans-1,4-cyclohexylene where one or two nonadjacent CH2 groups can be replaced by --O-- or --S-- and where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, (1,3,4)-thiadiazole-2,5-diyl, 1,3-thiazole-2,4-diyl, 1,3-thiazole-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, piperazine-1,4-diyl, piperazine-2,5-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, bicyclo[2.2.2]octane-1,4-diyl, 1,3-dioxaborinane-2,5-diyl or trans-decalin-2,6-diyl,
A2 and A3 can each be, independently of one another, 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, where one or two hydrogen atoms can be replaced by halogen atoms, cyano and/or methyl groups, 1,3,4-thiadiazole-2,5-diyl, 1,3-thiazole-2,4-diyl, 1,3-thiazole-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl or naphthalene-2,6-diyl,
M1 and M2 can each be, independently of one another, --O--, --S--, --CO--, --CO--O--, --O--CO--, --CO--S--, --S--CO--, --O--CO--O--, --CH2 --O--, --OCH2 --, --CH2 CH2 --, --CH═CH--, --C.tbd.C--, --CH(CN)--CH2 -- --CH2 --CH(CN)--, --CH═N--, --N═CH--, --CH2 CH2 CH2 --O--, --OCH2 CH2 CH2 --, --CH2 CH2 CO--O--, --O--COCH2 CH2 --,
k, l, m, n are each, independently of one another, zero or one, is prepared by reacting boronic acids of the formula II
R.sup.1 (--A.sup.1).sub.k (--M.sup.1).sub.l --A.sup.2 --B(OH).sub.2 (II)
where R1, A1, A2, M1, k and l are as defined above, with a compound of the formula (III)
X--A.sup.3 (--M.sup.2).sub.m (--A.sup.4).sub.n --R.sup.2   (III)
where R2, A3, A4, M2, m and n are as defined above, and X is chlorine, bromine, iodine or OSO2 --Cp F2p+1, where p is an integer from 1 to 10.
3. The process as claimed in claim 1, wherein the ligand is added in a proportion of 0.1-20 mol %, based on the aromatic halogen compound or the aromatic perfluoroalkylsulfonate.
4. The process as claimed in claim 1, wherein the base used is at least one compound selected from the group consisting of alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali metal and alkaline earth metal acetates, alkal metal and alkaline earth metal alkoxides and primary, secondary and tertiary amines.
5. The process as claimed in claim 4, wherein the base is used in a proportion of 100-500 mol %, based on the aromatic boronic acid.
6. The process as claimed in claim 1, carried out at temperatures between 50° and 150° C.
7. The process as claimed in claim 1, wherein the cross-coupling reaction is carried out in a solvent or solvent mixture which contains at least one compound selected from the group consisting of ethers, hydrocarbons, alcohols, ketones, amides, nitriles and water.
8. The process as claimed in claim 1, wherein the catalyst used is palladium in powdered form, palladium on activated carbon, palladium on aluminum oxide, palladium on barium sulfate or palladium on calcium carbonate, in each case having a palladium content of from 0.5 to 10% by weight.
US08/424,254 1992-10-26 1993-10-06 Process for cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates Expired - Fee Related US5550236A (en)

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US5820781A (en) * 1991-03-13 1998-10-13 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain & Northern Ireland Naphthyl organic compounds
US6232410B1 (en) 1997-08-27 2001-05-15 The Dow Chemical Company Elastomers with improved processability
US6265601B1 (en) 1998-08-06 2001-07-24 Symyx Technologies, Inc. Methods for using phosphine ligands in compositions for suzuki cross-coupling reactions
US6268513B1 (en) 1998-08-06 2001-07-31 Symyx Technologies, Inc. Phosphine ligands metal complexes and compositions thereof for cross-coupling reactions
US6353072B1 (en) 1999-03-05 2002-03-05 Cambridge Display Technology Limited Polymer preparation from boron derivative functional group-containing monomers
US6399779B1 (en) * 1997-04-09 2002-06-04 Commonwealth Scientific And Industrial Research Organisation Aryl borates
US20030091756A1 (en) * 2001-09-17 2003-05-15 Clariant International Ltd. Fluorinated cyclopenta[b]naphthalenes and their use in liquid-crystal mixtures
US20030108684A1 (en) * 2001-09-17 2003-06-12 Clariant International Ltd. Fluorinated cyclopenta[a]naphthalenes and their use in liquid-crystal mixtures
US6682785B2 (en) 2001-09-17 2004-01-27 Clariant Finance (Bvi) Limited Fluorinated anthracenes, and their use in liquid-crystal mixtures
US6939985B1 (en) 1997-04-09 2005-09-06 Commonwealth Scientific And Industrial Research Organisation Aryl borates
US20060030718A1 (en) * 2002-03-28 2006-02-09 University Of Tennessee Research Foundation Cobalt-based catalysts for the cyclization of alkenes
US20070161648A1 (en) * 2005-10-14 2007-07-12 Hughes Terry V Substituted dihydro-isoindolones useful in treating kinase disorders
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US20110172186A1 (en) * 2008-04-09 2011-07-14 Behnke Mark L Inhibitors of fatty acid amide hydrolase
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US5820781A (en) * 1991-03-13 1998-10-13 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain & Northern Ireland Naphthyl organic compounds
US5756804A (en) * 1995-07-25 1998-05-26 Hoechst Aktiengesellschaft Homogeneous process for carrying out cross-coupling reactions
US6399779B1 (en) * 1997-04-09 2002-06-04 Commonwealth Scientific And Industrial Research Organisation Aryl borates
US6939985B1 (en) 1997-04-09 2005-09-06 Commonwealth Scientific And Industrial Research Organisation Aryl borates
US6559310B2 (en) * 1997-04-09 2003-05-06 Commonwealth Scientific And Industrial Research Organisation Aryl borates
US6232410B1 (en) 1997-08-27 2001-05-15 The Dow Chemical Company Elastomers with improved processability
US6376620B2 (en) 1997-08-27 2002-04-23 The Dow Chemical Company Elastomers with improved processability
US6268513B1 (en) 1998-08-06 2001-07-31 Symyx Technologies, Inc. Phosphine ligands metal complexes and compositions thereof for cross-coupling reactions
US6265601B1 (en) 1998-08-06 2001-07-24 Symyx Technologies, Inc. Methods for using phosphine ligands in compositions for suzuki cross-coupling reactions
US6353072B1 (en) 1999-03-05 2002-03-05 Cambridge Display Technology Limited Polymer preparation from boron derivative functional group-containing monomers
US20030091756A1 (en) * 2001-09-17 2003-05-15 Clariant International Ltd. Fluorinated cyclopenta[b]naphthalenes and their use in liquid-crystal mixtures
US20030108684A1 (en) * 2001-09-17 2003-06-12 Clariant International Ltd. Fluorinated cyclopenta[a]naphthalenes and their use in liquid-crystal mixtures
US6682785B2 (en) 2001-09-17 2004-01-27 Clariant Finance (Bvi) Limited Fluorinated anthracenes, and their use in liquid-crystal mixtures
US6737125B2 (en) 2001-09-17 2004-05-18 Clariant Finance (Bvi) Limited Fluorinated cyclopenta[a]naphthalenes and their use in liquid-crystal mixtures
US6759103B2 (en) 2001-09-17 2004-07-06 Clariant Financi (Bvi) Limited Fluorinated cyclopenta[b]naphthalenes and their use in liquid-crystal mixtures
US20060030718A1 (en) * 2002-03-28 2006-02-09 University Of Tennessee Research Foundation Cobalt-based catalysts for the cyclization of alkenes
US20070161648A1 (en) * 2005-10-14 2007-07-12 Hughes Terry V Substituted dihydro-isoindolones useful in treating kinase disorders
WO2007047646A3 (en) * 2005-10-14 2007-09-27 Janssen Pharmaceutica Nv Substituted dihydro-isoindolones useful in treating kinase disorders
US7947663B2 (en) 2006-10-10 2011-05-24 Infinity Pharmaceuticals, Inc. Inhibitors of fatty acid amide hydrolase
US9108989B2 (en) 2006-10-10 2015-08-18 Infinity Pharmaceuticals, Inc. Inhibitors of fatty acid amide hydrolase
US20090099131A1 (en) * 2006-10-10 2009-04-16 Infinity Discovery, Inc. Inhibitors of fatty acid amide hydrolase
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US20110224171A1 (en) * 2006-10-10 2011-09-15 Julian Adams Inhibitors of fatty acid amide hydrolase
US20110230440A1 (en) * 2006-10-10 2011-09-22 Julian Adams Inhibitors of fatty acid amide hydrolase
US8329675B2 (en) 2006-10-10 2012-12-11 Infinity Pharmaceuticals, Inc. Inhibitors of fatty acid amide hydrolase
US20110172186A1 (en) * 2008-04-09 2011-07-14 Behnke Mark L Inhibitors of fatty acid amide hydrolase
US8957049B2 (en) 2008-04-09 2015-02-17 Infinity Pharmaceuticals, Inc. Inhibitors of fatty acid amide hydrolase
WO2010112799A1 (en) 2009-02-26 2010-10-07 University Of York Luminophores comprising platinum-ligand complexes
US8541581B2 (en) 2009-04-07 2013-09-24 Infinity Pharmaceuticals, Inc. Inhibitors of fatty acid amide hydrolase
US8546564B2 (en) 2009-04-07 2013-10-01 Infinity Pharmaceuticals, Inc. Inhibitors of fatty acid amide hydrolase
US8802119B2 (en) 2009-04-07 2014-08-12 Infinity Pharmaceuticals, Inc. Inhibitors of fatty acid amide hydrolase
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US20110201574A1 (en) * 2010-02-03 2011-08-18 Austad Brian C Fatty acid amide hydrolase inhibitors
US9034849B2 (en) 2010-02-03 2015-05-19 Infinity Pharmaceuticals, Inc. Fatty acid amide hydrolase inhibitors
US8962779B2 (en) 2013-07-16 2015-02-24 Dow Global Technologies Llc Method of forming polyaryl polymers
US9063420B2 (en) 2013-07-16 2015-06-23 Rohm And Haas Electronic Materials Llc Photoresist composition, coated substrate, and method of forming electronic device
US9410016B2 (en) 2013-07-16 2016-08-09 Dow Global Technologies Llc Aromatic polyacetals and articles comprising them
US8933239B1 (en) 2013-07-16 2015-01-13 Dow Global Technologies Llc Bis(aryl)acetal compounds
US9580651B2 (en) 2013-07-30 2017-02-28 Semiconductor Energy Laboratory Co., Ltd. Organic compound, liquid crystal composition, liquid crystal element, and liquid crystal display device
US11078528B2 (en) 2015-10-12 2021-08-03 Advanced Cell Diagnostics, Inc. In situ detection of nucleotide variants in high noise samples, and compositions and methods related thereto
US10246393B2 (en) * 2016-10-31 2019-04-02 Tosoh Corporation Method for producing aromatic compound

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DE59305175D1 (en) 1997-02-27
WO1994010105A1 (en) 1994-05-11
EP0665825B1 (en) 1997-01-15
KR0147697B1 (en) 1998-08-17
JP2736172B2 (en) 1998-04-02
JPH08501107A (en) 1996-02-06
DE4236103A1 (en) 1994-04-28
KR950704213A (en) 1995-11-17

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